CN110563944B

CN110563944B - Polyphosphazene covalent triazine polymer and preparation method and application thereof

Info

Publication number: CN110563944B
Application number: CN201910938596.2A
Authority: CN
Inventors: 王贵友; 方云志; 朱芸
Original assignee: East China University of Science and Technology
Current assignee: East China University of Science and Technology
Priority date: 2019-09-30
Filing date: 2019-09-30
Publication date: 2022-09-27
Anticipated expiration: 2039-09-30
Also published as: CN110563944A

Abstract

The invention discloses a polyphosphazene covalent triazine polymer and a preparation method and application thereof. The invention takes a phosphonitrile derivative with a cyano-containing end group as a precursor, and performs cyclotrimerization reaction under the catalysis of protonic acid to prepare the covalent triazine polymer with the phosphorus nitrile structure. The polyphosphazene covalent triazine polymer prepared by the invention has the characteristics of simple preparation process, mild reaction conditions, good thermal stability and the like. When the prepared polyphosphazene covalent triazine polymer is applied to the flame retardant aspect of epoxy resin, a synergistic flame retardant effect exists, the flame retardant efficiency is high, the mechanical property of the epoxy resin cannot be damaged, and the flame retardant has a high practical application value.

Description

Polyphosphazene covalent triazine polymer and preparation method and application thereof

Technical Field

The invention belongs to the technical field of high molecular materials, and particularly relates to a polyphosphazene covalent triazine polymer and a preparation method and application thereof.

Background

Epoxy resin is widely applied to the fields of household appliances, transportation, construction, agriculture and the like, but the application of the epoxy resin in the fields of some electronics, electric appliances, automobiles, aviation, aerospace and the like is limited due to the defect of flammability. In order to reduce the potential safety hazard, people urgently need to design a high-efficiency flame retardant and use the flame retardant to effectively improve the flame resistance of the epoxy resin.

Halogen, phosphorus and nitrogen flame retardants have been the focus of research in the field of flame retardancy, but halogen flame retardants harmful to the human body are gradually limited in their application. With the development of science and technology and the trend of people to meet the requirements of good life, a single-component flame retardant can not meet the requirements of high-performance flame retardant materials, so that a plurality of synergistic flame retardants come into play, wherein the nitrogen/phosphorus synergistic flame retardant is widely concerned due to the characteristics of greenness, no toxicity, high efficiency and the like. Hexachlorocyclotriphosphazene (HCCP) is a typical organic-inorganic hybrid material, and phosphorus and nitrogen in the skeleton can provide abundant nitrogen and phosphorus sources. Due to the higher activity of P-Cl group, HCCP can derive a series of phosphazene flame retardants, and among them, phosphazene derivatives linked with nitrogen-containing heterocycles (such as maleimide, triazole and triazine) are receiving attention due to the better nitrogen/phosphorus synergistic effect. However, most of the phosphazene derivatives containing nitrogen heterocycles are small molecules, and the preparation process is complicated; in addition, the phosphazene derivative containing the nitrogen heterocycle is usually required to be compounded with other flame retardants such as ammonium polyphosphate and the like for use to achieve a good flame retardant effect, so that the practical application of the phosphazene derivative is greatly limited. In addition, in order to achieve a better flame retardant effect, a large amount of phosphazene-based flame retardant is usually added to the polymer base material, so that the mechanical properties of the polymer base material are greatly damaged. In view of the above, it is urgent to find a nitrogen/phosphorus synergistic flame retardant which is satisfactory for practical use, highly effective and does not impair mechanical properties of polymer substrates.

Disclosure of Invention

Aiming at the defects of the prior art, the invention aims to provide a preparation method and application of a polyphosphazene covalent triazine polymer. The compound has simple preparation process, high flame retardant efficiency when used as a flame retardant, and no damage to the mechanical properties of a polymer base material.

The polyphosphazene covalent triazine polymer has the following structure:

wherein the content of the first and second substances,

represents a repeating structural unit;

n is an integer of 0 to 4;

r is any one of the following structures;

wherein n is an integer of 0 to 4.

The preparation method and the application of the polyphosphazene covalent triazine polymer comprise the following steps:

step 1: dissolving hexachlorocyclotriphosphazene and cyanophenol or a mixture of cyanophenol and monophenol in an organic solvent in proportion, reacting for a period of time under the action of an acid-binding agent, and removing residual salt and the solvent to obtain a cyano-containing phosphazene compound M.

Step 2: and (2) dispersing the cyano-containing phosphazene compound M obtained in the step (1) in an organic solvent, keeping the temperature at-20-0 ℃, gradually dripping a protonic acid catalyst into the mixture under stirring and anhydrous and anaerobic conditions, reacting for 2 hours at-20-0 ℃ within 30-120 min, and then heating for reaction for a period of time.

And step 3: and (3) slowly adding an alkaline solution into the mixture obtained in the step (2), adjusting the pH of the system to be neutral, and keeping the pH for 1-5 hours. Then carrying out suction filtration, washing and drying to obtain the polyphosphazene covalent triazine polymer Z.

The above process can be expressed by the chemical equation:

wherein X is a cyanophenol, Y is a monohydric phenol, and X is essential, and Y is used as a terminal block and is optional. x is H, -CHO, -Br, ‒ OCH ₃ ，–CH ₂ One of OH.

In the step 1, the molar ratio of hexachlorocyclotriphosphazene to cyanophenol is 1: 6-10, wherein the molar ratio of the mixture of hexachlorocyclotriphosphazene, cyanophenol and monohydric phenol is 1: x: (6-x), wherein x is an integer of 2-4.

In the step 1, the organic solvent is any one of tetrahydrofuran, acetone and chloroform.

In the step 1, the acid-binding agent is any one of triethylamine, potassium carbonate, sodium carbonate or cesium carbonate. The molar ratio of the acid-binding agent to hexachlorocyclotriphosphazene is 6-15: 1.

in the step 1, reacting for a period of time under the action of an acid binding agent under the reaction condition of room temperature-65 ℃ for 5-100 h.

In the step 2, the organic solvent is any one or more of dichloromethane, o-xylene, chloroform or o-dichlorobenzene.

In the step 2, the protonic acid catalyst is any one of trifluoromethanesulfonic acid, ammonium trifluoromethanesulfonate, methanesulfonic acid or chlorosulfonic acid. The molar ratio of the cyano-containing phosphazene compound M to the protonic acid catalyst is 1: 4 to 10.

In the step 2, the temperature is raised and the reaction is carried out for a period of time, wherein the reaction temperature is room temperature to 120 ℃, and the period of time is 12 to 24 hours.

In the step 3, the alkaline solution is any one of an ammonia water solution, a sodium hydroxide solution or a potassium hydroxide solution.

In the step 3, the concentration of the alkaline solution is 0.1-2 mol/L.

In the step 3, the solvent used in the washing process is any one or more of deionized water, methanol, ethanol, tetrahydrofuran or acetone.

Compared with the prior art, the invention has the following beneficial effects:

1. the polyphosphazene covalent triazine polymer provided by the invention is a macromolecular crosslinking structure and has excellent thermal stability and carbon forming performance. Meanwhile, the triazine unit is formed by covalent bonding, an effective nitrogen source is provided, and the synergistic flame retardant effect is achieved.

2. The polyphosphazene covalent triazine polymer provided by the invention has higher flame retardant property to epoxy resin, and can greatly reduce the heat release rate and the total smoke release amount of a base material in the combustion process under the condition of lower additive amount (2-8 wt%). Meanwhile, the mechanical property of the epoxy resin substrate is not damaged.

3. The polyphosphazene covalent triazine polymer provided by the invention has the advantages of simple preparation process, mild reaction conditions, easiness in post-treatment and larger practical application potential.

Drawings

FIG. 1 shows the IR spectra of the cyano group-containing phosphazene compound and polyphosphazene covalent triazine polymer in example 1 of the present invention.

FIG. 2 is an X-ray photoelectron spectrum of the polyphosphazene covalent triazine polymer of example 1.

FIG. 3 is a thermogravimetric plot of polyphosphazene covalent triazine polymer of example 1 of the present invention.

FIG. 4 is a graph showing the heat release rate of the flame retardant epoxy resin in example 12 of the present invention.

FIG. 5 is a graph showing the total heat release of the flame retardant epoxy resin in example 12 of the present invention.

Detailed Description

The present invention will be described in detail with reference to specific examples. The present embodiment is implemented on the premise of the technical solution of the present invention, and a detailed implementation manner and a specific operation process are given, but the scope of the present invention is not limited to the following embodiments.

Example 1

(1) Under the protection of nitrogen, 57.44 mmol of HCCP, 344.8 mmol of 4-hydroxybenzonitrile and 828 mmol of potassium carbonate are dissolved in 800 mL of acetone, then the mixture reacts at 55 ℃ for 10 hours, after the reaction is finished, excess solvent is removed by rotary evaporation, the mixture is washed for a plurality of times by a large amount of deionized water, then the suction filtration is carried out, and the crude product is recrystallized and dried to obtain the cyano-containing phosphazene compound M1.

(2) Under the protection of nitrogen, 18.5 mmol of phosphonitrile compound M1 containing cyano is dispersed in chloroform, the temperature is controlled at 0 ℃, 120 mmol of trifluoromethanesulfonic acid is gradually added dropwise into the system by using a constant pressure dropping funnel, the dropping is completed within 30 min, the reaction is kept at 0 ℃ for 2h, and then the reaction is carried out at room temperature for 22 h. After the reaction is finished, adding 1.0 mol/L ammonia water solution, adjusting the pH of the system to be neutral, and stirring for 2 h. Finally, the obtained product is filtered, washed with deionized water, ethanol and tetrahydrofuran for a plurality of times and dried to obtain the final product Z1.

And performing infrared and X-ray photoelectron spectroscopy and thermogravimetric analysis on the polyphosphazene covalent triazine polymer. The results are shown in FIGS. 1, 2 and 3.

FIG. 1 shows an infrared spectrum of a cyano group-containing phosphazene compound M1 and a polyphosphazene covalent triazine polymer Z1 provided in example 1 of the present invention. As can be seen from FIG. 1, Z1, compared to M1, has wave numbers of 1677 and 1366 cm ^-1 Two new absorption peaks are generated, and the generation of the triazine ring is proved; at the same time, is located at 2232 cm ^-1 The peak intensity of cyano group is obviously reduced, showing thatThe polymerization reaction occurs.

FIG. 2 is an X-ray photoelectron spectrum of polyphosphazene covalent triazine polymer Z1 provided in example 1 of the present invention. As can be seen from fig. 2, the C1 s spectrum of Z1 has binding energies of 286.3 and 284.6 eV, corresponding to C = N and C = C, respectively; whereas in the N1 s spectrum the signal at 398.8 eV is derived from C = N-C, indicating the presence of the triazine unit in Z1.

Fig. 3 is a thermogravimetric graph of polyphosphazene covalent triazine polymer Z1 provided in example 1 of the present invention, and it can be seen from fig. 3 that Z1 has high thermal stability, and its residual carbon content at 800 ℃ is up to 67%.

Example 2

(1) Under the protection of nitrogen, 57.44 mmol of HCCP, 344.8 mmol of 4-hydroxy-biphenylnitrile and 828 mmol of triethylamine are dissolved in 800 mL of acetone, then the mixture reacts for 24 hours at 55 ℃, after the reaction is finished, excess solvent is removed by rotary evaporation, and the mixture is washed for a plurality of times by a large amount of deionized water, and then the suction filtration is carried out, and the crude product is recrystallized and dried to obtain the cyano-containing phosphazene compound M2.

(2) Under the protection of nitrogen, 18.5 mmol of phosphonitrile compound M2 containing cyano is dispersed in chloroform, the temperature is controlled at 0 ℃, 120 mmol of trifluoromethanesulfonic acid is gradually added dropwise into the system by using a constant pressure dropping funnel, the dropping is completed within 30 min, the reaction is kept at 0 ℃ for 2h, and then the reaction is carried out at room temperature for 22 h. After the reaction is finished, adding 0.5 mol/L ammonia water solution, adjusting the pH of the system to be neutral, and stirring for 2 h. Finally, the obtained product is filtered, washed with deionized water, ethanol and tetrahydrofuran for a plurality of times and dried to obtain the final product Z2.

Example 3

(1) Under the protection of nitrogen, 57.44 mmol of HCCP, 172.4 mmol of 4-hydroxybenzonitrile, 172.4 mmol of phenol and 828 mmol of potassium carbonate are dissolved in 800 mL of acetone, then the mixture reacts at 55 ℃ for 48 hours, after the reaction is finished, excessive solvent is removed by rotary evaporation, the mixture is washed by a large amount of deionized water for a plurality of times, then suction filtration is carried out, and the crude product is recrystallized and dried to obtain the cyano-containing phosphazene compound M3.

(2) Under the protection of nitrogen, 18.5 mmol of cyano-containing phosphazene compound M3 is dispersed in chloroform, the temperature is controlled at 0 ℃, 90 mmol of trifluoromethanesulfonic acid is gradually dripped into the system by using a constant pressure dropping funnel, the dripping is finished within 30 min, the reaction is kept at 0 ℃ for 2h, and then the reaction is carried out at room temperature for 22 h. After the reaction is finished, adding 0.5 mol/L ammonia water solution, adjusting the pH of the system to be neutral, and stirring for 2 h. Finally, the obtained product is filtered, washed with deionized water, ethanol and tetrahydrofuran for a plurality of times and dried to obtain the final product Z3.

Example 4

(1) Under the protection of nitrogen, 57.44 mmol of HCCP, 114.9 mmol of 4-hydroxybenzonitrile, 229.8 mmol of phenol and 828 mmol of cesium carbonate are dissolved in 800 mL of acetone, then the mixture reacts at 55 ℃ for 67 hours, after the reaction is finished, excess solvent is removed by rotary evaporation, the mixture is washed for a plurality of times by a large amount of deionized water, then the suction filtration is carried out, and the crude product is recrystallized and dried to obtain the cyano-containing phosphazene compound M4.

(2) Under the protection of nitrogen, 18.5 mmol of phosphazene compound M4 containing a cyano group is dispersed in chloroform, the temperature is controlled at 0 ℃, 90 mmol of trifluoromethanesulfonic acid is gradually added dropwise into the system by using a constant pressure dropping funnel, the dropwise addition is completed within 30 min, the reaction is kept at 0 ℃ for 2h, and then the reaction is carried out at room temperature for 22 h. After the reaction is finished, adding 0.5 mol/L potassium hydroxide solution, adjusting the pH of the system to be neutral, and stirring for 2 h. Finally, the obtained product is filtered, washed with deionized water, ethanol and tetrahydrofuran for a plurality of times and dried to obtain the final product Z4.

Example 5

(1) Under the protection of nitrogen, 57.44 mmol of HCCP, 172.4 mmol of 4-hydroxybenzonitrile, 172.4 mmol of 4-hydroxybenzaldehyde and 828 mmol of potassium carbonate are dissolved in 800 mL of tetrahydrofuran, then the reaction is carried out for 48 h at 60 ℃, after the reaction is finished, excessive solvent is removed by rotary evaporation, a large amount of deionized water is used for washing for a plurality of times, then suction filtration is carried out, and the crude product is recrystallized and dried to obtain the cyano-containing phosphazene compound M5.

(2) Under the protection of nitrogen, 18.5 mmol of cyano-containing phosphazene compound M5 is dispersed in chloroform, the temperature is controlled at 0 ℃, 90 mmol of trifluoromethanesulfonic acid is gradually dripped into the system by using a constant pressure dropping funnel, the dripping is finished within 30 min, the reaction is kept at 0 ℃ for 2h, and then the reaction is carried out at room temperature for 22 h. After the reaction is finished, 0.5 mol/L ammonia water solution is added, the pH value of the system is adjusted to be neutral, and the mixture is stirred for 2 hours. Finally, the obtained product is filtered, washed with deionized water, ethanol and tetrahydrofuran for a plurality of times and dried to obtain the final product Z5.

Example 6

(1) Under the protection of nitrogen, 57.44 mmol of HCCP, 172.4 mmol of 4-hydroxybenzonitrile, 172.4 mmol of 4-bromophenol and 828 mmol of potassium carbonate are dissolved in 800 mL of acetone, then the mixture reacts at room temperature for 5 hours, after the reaction is finished, excess solvent is removed by rotary evaporation, the mixture is washed by a large amount of deionized water for a plurality of times, then the suction filtration is carried out, and the crude product is recrystallized and dried to obtain the cyano-containing phosphazene compound M6.

(2) Under the protection of nitrogen, 18.5 mmol of cyano-containing phosphazene compound M6 is dispersed in chloroform, the temperature is controlled at 0 ℃, 100 mmol of trifluoromethanesulfonic acid is gradually dripped into the system by using a constant pressure dropping funnel, the dripping is finished within 30 min, the reaction is kept at 0 ℃ for 2h, and then the reaction is carried out at room temperature for 24 h. After the reaction is finished, adding 0.5 mol/L ammonia water solution, adjusting the pH of the system to be neutral, and stirring for 2 h. Finally, the obtained product is filtered, washed with deionized water, ethanol and tetrahydrofuran for a plurality of times and dried to obtain the final product Z6.

Example 7

(1) Under the protection of nitrogen, 57.44 mmol of HCCP, 172.4 mmol of 4-hydroxybenzonitrile, 172.4 mmol of 4-hydroxybenzyl alcohol and 828 mmol of potassium carbonate are dissolved in 800 mL of tetrahydrofuran, and then react for 96 h at 55 ℃, after the reaction is finished, excessive solvent is removed by rotary evaporation, and the solvent is washed by a large amount of deionized water for a plurality of times, and then suction filtration is carried out, and the crude product is recrystallized and dried to obtain the cyano-containing phosphazene compound M7.

(2) Under the protection of nitrogen, 18.5 mmol of phosphonitrile compound M7 containing cyano is dispersed in chloroform, the temperature is controlled at 0 ℃, 100 mmol of trifluoromethanesulfonic acid is gradually dripped into the system by using a constant pressure dropping funnel within 30 min, the reaction is carried out for 2h while the temperature is kept at 0 ℃, and then the reaction is carried out for 22 h at room temperature. After the reaction is finished, 0.5 mol/L sodium hydroxide solution is added, the pH of the system is adjusted to be neutral, and the mixture is stirred for 2 hours. Finally, the obtained product is filtered, washed with deionized water, ethanol and tetrahydrofuran for a plurality of times and dried to obtain the final product Z7.

Example 8

(1) Under the protection of nitrogen, 57.44 mmol of HCCP, 344.8 mmol of 4-hydroxybenzonitrile and 828 mmol of cesium carbonate are dissolved in 800 mL of acetone, then the mixture reacts at 55 ℃ for 10 hours, after the reaction is finished, excess solvent is removed by rotary evaporation, the mixture is washed for a plurality of times by a large amount of deionized water, then the suction filtration is carried out, and the crude product is recrystallized and dried to obtain the cyano-containing phosphazene compound M8.

(2) Under the protection of nitrogen, 18.5 mmol of phosphonitrile compound M8 containing cyano is dispersed in o-dichlorobenzene, the temperature is controlled at 0 ℃, 120 mmol of trifluoromethanesulfonic acid is gradually added dropwise into the system by using a constant pressure dropping funnel, the reaction is completed within 30 min, the reaction is kept at 0 ℃ for 2h, and then the reaction is carried out at room temperature for 24 h. After the reaction is finished, adding 1.0 mol/L ammonia water solution, adjusting the pH of the system to be neutral, and stirring for 2 h. Finally, the obtained product is filtered, washed with deionized water, ethanol and tetrahydrofuran for a plurality of times and dried to obtain the final product Z8.

Example 9

(1) Under the protection of nitrogen, 57.44 mmol of HCCP, 344.8 mmol of 4-hydroxybenzonitrile and 828 mmol of sodium carbonate are dissolved in 800 mL of acetone, then the mixture reacts at 55 ℃ for 20 hours, after the reaction is finished, excessive solvent is removed by rotary evaporation, the mixture is washed by a large amount of deionized water for a plurality of times, then suction filtration is carried out, and the crude product is recrystallized and dried to obtain the cyano-containing phosphazene compound M9.

(2) Under the protection of nitrogen, 18.5 mmol of phosphazene compound M9 containing a cyano group is dispersed in o-dichlorobenzene, the temperature is controlled at 0 ℃, 120 mmol of ammonium trifluoromethanesulfonate is gradually dripped into the system by using a constant pressure dropping funnel within 30 min, the reaction is carried out for 2h while the temperature is kept at 0 ℃, and then the reaction is carried out for 24h at room temperature. After the reaction is finished, adding 0.2 mol/L sodium hydroxide solution, adjusting the pH of the system to be neutral, and stirring for 2 hours. Finally, the obtained product is filtered, washed with deionized water, ethanol and tetrahydrofuran for a plurality of times and dried to obtain the final product Z9.

Example 10

(1) Under the protection of nitrogen, 57.44 mmol of HCCP, 114.9 mmol of 4-hydroxy-biphenylnitrile, 229.8 mmol of 4-bromophenol and 828 mmol of cesium carbonate are dissolved in 800 mL of acetone, then the mixture reacts for 20 hours at 55 ℃, after the reaction is finished, excess solvent is removed by rotary evaporation, and the mixture is washed for a plurality of times by a large amount of deionized water, and then the suction filtration is carried out, and the crude product is recrystallized and dried to obtain the cyano-containing phosphazene compound M10.

(2) Under the protection of nitrogen, 18.5 mmol of phosphonitrile compound M10 containing cyano is dispersed in o-dichlorobenzene, the temperature is controlled at 0 ℃, 120 mmol of trifluoromethanesulfonic acid is gradually dripped into the system by using a constant pressure dropping funnel within 30 min, the reaction is carried out for 2h while the temperature is kept at 0 ℃, and then the reaction is carried out for 24h at 120 ℃. After the reaction is finished, 0.5 mol/L sodium hydroxide solution is added, the pH of the system is adjusted to be neutral, and the mixture is stirred for 2 hours. Finally, the obtained product is filtered, washed with deionized water, ethanol and tetrahydrofuran for a plurality of times and dried to obtain the final product Z10.

Example 11

(1) Under the protection of nitrogen, 57.44 mmol of HCCP, 114.9 mmol of 4-hydroxy-biphenylnitrile, 229.8 mmol of 4-hydroxybenzaldehyde and 828 mmol of potassium carbonate are dissolved in 800 mL of acetone, then the mixture reacts for 48 hours at 55 ℃, after the reaction is finished, excess solvent is removed by rotary evaporation, and the mixture is washed for a plurality of times by a large amount of deionized water, and then suction filtration is carried out, and the crude product is recrystallized and dried to obtain the cyano-containing phosphazene compound M11.

(2) Under the protection of nitrogen, 18.5 mmol of phosphazene compound M11 containing a cyano group is dispersed in dichloromethane, the temperature is controlled at-10 ℃, 120 mmol of trifluoromethanesulfonic acid is gradually dripped into the system by using a constant pressure dropping funnel, the dripping is completed within 30 min, the reaction is kept at-10 ℃ for 2h, and then the reaction is carried out at room temperature for 24 h. After the reaction is finished, 1.0 mol/L ammonia water solution is added, the pH value of the system is adjusted to be neutral, and the mixture is stirred for 2 hours. Finally, the obtained product is filtered, washed with deionized water, ethanol and tetrahydrofuran for a plurality of times and dried to obtain the final product Z11.

Example 12

In this example, polyphosphazene covalent triazine polymer Z1 prepared in example 1 was used for flame retardancy of epoxy resin. The preparation route of the composite material is as follows: the polyphosphazene covalent triazine polymer obtained in the example 1 with the mass fraction of 4-8 wt% is ground and then dispersed in tetrahydrofuran, and then the mixture and epoxy resin are ultrasonically stirred for 3 hours at 60 ℃. The solvent was removed in vacuo and the curing agent 4, 4' -diaminodiphenylmethane was added. And after uniformly mixing, immediately pouring the mixture into a preheated mold, and curing for 2 hours at 100 ℃ and 2 hours at 150 ℃ to obtain the flame-retardant epoxy resin composite material.

Cone calorimetry was performed on the above flame retardant epoxy resin composite, and the results were shown in fig. 4 and 5.

Fig. 4 and 5 are respectively a heat release rate curve (HRR) and a total heat release curve (THR) of the flame-retardant epoxy resin composite material provided in example 12 of the present invention, and it can be seen from fig. 4 and 5 that as the content of Z1 is increased, the peak heat release rate (P-HRR) and the THR value of the composite material are greatly reduced, and when the amount of Z1 added is 8 wt%, the P-HRR and the THR value are reduced by 73% and 69% respectively compared with those of a pure epoxy resin, which indicates that the prepared polyphosphazene covalent triazine polymer has excellent flame retardant performance on the epoxy resin.

The mechanical properties of the flame-retardant epoxy resin composite material were analyzed, and the results are shown in table 1.

TABLE 1

Sample (I)	Tensile Strength (MPa)	Elongation at Break (%)	Tensile modulus (GPa)	Flexural Strength (MPa)	Flexural modulus (GPa)
						EP	63.7±2.4	11.2±2.0	1.07±0.05	115.1±7.8	3.55±0.19
EP@Z1-4	70.9±1.5	8.8±0.3	1.10±0.09	119.8±3.7	3.61±0.20
						EP@Z1-6	68.6±1.2	8.5±0.2	1.15±0.03	121.0±4.2	3.77±0.23
EP@Z1-8	64.3±1.7	7.8±0.2	1.18±0.04	114.6±1.2	3.90±0.10

Table 1 shows the mechanical property data of the flame retardant epoxy resin composite material provided in example 12 of the present invention, and it can be seen from the data in the table that the mechanical properties of the epoxy resin composite material added with the polyphosphazene covalent triazine polymer of the present invention are not damaged, which indicates that the epoxy resin composite material has good compatibility with the epoxy resin substrate.

The embodiments described above are intended to facilitate the understanding and use of the invention by those skilled in the art. It will be readily apparent to those skilled in the art that various modifications to these embodiments may be made, and the generic principles described herein may be applied to other embodiments without the use of the inventive faculty. Therefore, the present invention is not limited to the above embodiments, and those skilled in the art should make modifications and alterations without departing from the scope of the present invention.

Claims

1. A polyphosphazene covalent triazine polymer, wherein the polyphosphazene covalent triazine polymer has the structure:

wherein the content of the first and second substances,

represents a repeating structural unit;

n is an integer of 0 to 4;

r is any one of the following structures;

wherein n is an integer of 0 to 4.

2. A method of preparing a polyphosphazene covalent triazine polymer according to claim 1, comprising the steps of:

step 1: dissolving hexachlorocyclotriphosphazene and cyanophenol or a mixture of cyanophenol and monophenol in an organic solvent in proportion, reacting for a period of time under the action of an acid-binding agent, and removing residual salt and the solvent to obtain a cyano-containing phosphazene compound M;

step 2: dispersing the phosphazene compound M containing the cyano group obtained in the step 1 in an organic solvent, keeping the temperature at-20-0 ℃, gradually dripping a protonic acid catalyst into the mixture under the conditions of stirring, no water and no oxygen, keeping the temperature at-20-0 ℃ for reacting for 2 hours within 30-120 min, and then heating for reacting for a period of time;

and 3, step 3: slowly adding an alkaline solution into the mixture obtained in the step 2, adjusting the pH value of the system to be neutral, and keeping for 1-5 h; then, carrying out suction filtration, washing and drying to obtain polyphosphazene covalent triazine polymer Z;

the above process can be expressed by the chemical equation:

wherein n is an integer of 0 to 4, X is cyanophenol, Y is monophenol, and X is essential, and Y is optional and used as an end cap; x is H, -CHO, -Br, -OCH ₃ ，–CH ₂ One of OH.

3. The method according to claim 2, wherein the molar ratio of hexachlorocyclotriphosphazene to cyanophenol in step 1 is 1: 6-10, wherein the molar ratio of the mixture of hexachlorocyclotriphosphazene, cyanophenol and monohydric phenol is 1: m: (6-m), wherein m is an integer of 2-4.

4. The method according to claim 2, wherein in step 1, the organic solvent is any one of tetrahydrofuran, acetone, and chloroform.

5. The preparation method according to claim 2, wherein in the step 1, the acid-binding agent is any one of triethylamine, potassium carbonate, sodium carbonate or cesium carbonate.

6. The preparation method of claim 2, wherein in the step 1, the molar ratio of the acid-binding agent to hexachlorocyclotriphosphazene is 6-15: 1.

7. the preparation method according to claim 2, wherein in the step 1, the temperature is raised under the action of an acid-binding agent for reaction for a period of time, and the reaction condition is room temperature to 65 ℃ for 5 to 100 hours.

8. The method according to claim 2, wherein in the step 2, the organic solvent is any one or more of dichloromethane, o-xylene, chloroform or o-dichlorobenzene.

9. The method according to claim 2, wherein in step 2, the protonic acid catalyst is any one of trifluoromethanesulfonic acid, ammonium trifluoromethanesulfonate, methanesulfonic acid, and chlorosulfonic acid.

10. The method according to claim 2, wherein in step 2, the molar ratio of the cyano group-containing phosphazene compound M to the protonic acid catalyst is 1: 4 to 10.

11. The preparation method according to claim 2, wherein in the step 2, the temperature is raised for a period of time, the reaction temperature is room temperature to 120 ℃, and the period of time is 12 to 24 hours.

12. The method according to claim 2, wherein in step 3, the alkaline solution is any one of an aqueous ammonia solution, a sodium hydroxide solution, and a potassium hydroxide solution.

13. The method according to claim 2, wherein the concentration of the alkaline solution in step 3 is 0.1 to 2 mol/L.

14. The method according to claim 2, wherein in step 3, the solvent used in the washing process is any one or more of deionized water, methanol, ethanol, tetrahydrofuran, and acetone.

15. Use of a polyphosphazene covalent triazine polymer according to claim 1 or prepared by a method according to any one of claims 2 to 14 as an additive flame retardant in an epoxy resin matrix to improve the flame retardant and mechanical properties of the epoxy resin.

16. The use of claim 15, wherein when the polyphosphazene covalent triazine polymer is added to the epoxy resin at 8 wt%, the limiting oxygen index is 28%, and the peak heat release rate (P-HRR) and Total Heat Release (THR) are reduced by 73% and 69%, respectively, when the poiyphosphazene covalent triazine polymer passes UL-94 test V-0 rating.